Substituted tricyclodecane derivatives, processes for producing same and organoleptic uses thereof

ABSTRACT

Described are substituted tricyclodecane derivatives having the generic structure: ##STR1## wherein Y is a moiety having a structure selected from the group consisting of: ##STR2## wherein one of the dashed lines represents a carbon-carbon single bond and the other of the dashed lines represents a carbon-carbon double bond; wherein R 1  and R 2  represent hydrogen or methyl with the proviso that one of R 1  and R 2  is hydrogen and the other of R 1  and R 2  is methyl; wherein R 3  is hydrogen, C 1  -C 3  acyl, C 3  or C 4  alkyl or C 3  or C 4  alkenyl; wherein R 4 , R 5  and R 6  represent hydrogen or methyl with the additional proviso that one of R 4 , R 5  and R 6  is methyl and the other two of R 4 , R 5  and R 6  is hydrogen. Also described are processes for preparing such substituted tricyclodecane derivatives and processes for using the above defined substituted tricyclodecane derivatives for their organoleptic properties and compositions containing said substituted tricyclodecane derivatives including perfumes, perfumed articles, such as solid or liquid anionic, cationic, nonionic and zwitterionic detergents, fabric softeners and cosmetic powders; foodstuffs, chewing gums, toothpastes, medicinal products and chewing tobaccos; smoking tobacco compositions and smoking tobacco flavoring compositions and smoking tobacco articles containing such smoking tobacco compositions.

This is a divisional of application Ser. No. 220,628, filed Dec. 29,1980, now abandoned, which in turn, is a divisional of U.S. LettersPatent, Ser. No. 144,898 filed on Apr. 29, 1980 now U.S. Pat. No.4,275,251 issued June 23, 1981.

BACKGROUND OF THE INVENTION

Materials including mixtures of natural products which can providepatchouli-like, green, floral, musty/camphoraceous, rosey, woody,anisic, ionone-like, fruity (banana-like), spicey (cinnamon-like),bitter sweet, milky, petitgrain-like, lavender, bergamot-like, fatty andminty fragrance notes are known in the art of perfumery. Many of thenatural materials which provide such fragrances and contribute desirednuances to perfumery compositions are high in cost, vary in quality fromone batch to another and/or are generally subject to the usualvariations in natural products.

There is, accordingly, a continuing effort to find synthetic materialswhich will replace the essential fragrance notes provided by naturalessential oils or compositions thereof. Unfortunately, many of thesesynthetic materials either have the desired nuances only to a relativelysmall degree or else contribute undesirable or unwanted odor to thecompositions. The search for materials which can provide a more refinedpatchouli-like fragrance, for example, has been difficult and relativelycostly in the areas of both natural products and synthetic products.

Thus, Light, et al in U.S. Pat. No. 3,989,760 provides processes andcompositions for altering the flavor and/or aroma of consumableproducts, including foods, tobacco and perfumes, particularly, perfumeshaving a patchouli aroma, utilizing as the essential ingredient theorganic tricyclic alcohol having the formula: ##STR3##

Buchi, et al., 83 J. Am. Chem. Soc. 927 (1961), shows the production ofa material called "patchoulione" which is stated to beoctahydro-1,4,9,9-tetramethyl-3a,7-methanoazulen-5-(4H)-one having thestructure: ##STR4##

U.S. Pat. No. 3,748,284 issued on July 24, 1973 discloses perhydroderivatives of methanoazulen as having camphoraceous woody fragrancesand having the ability to impart this fragrance to perfumed compositionsand perfumed articles. The compounds disclosed are:

a. Octahydro-1,4,9,9-tetramethyl-4,7-methanoazulen-3(2H)-one;

b. Octahydro-1,4,9,9-tetramethyl-4,7-methanoazulen-3(3H)-one; and

c. Octahydro-1,4,9,9-tetramethyl-4,7-methanoazulen-8(7H)-one.

Umarani, et al., Sept./Oct. 1969, P. & E.O.R., 307 discloses twocompounds relevant to the instant case:

"isopatchoulinol" having the structure: ##STR5## and "patchouli alcohol"having the structure: ##STR6##

In addition, artificial flavoring agents for foodstuffs have receivedincreasing attention in recent years. In many years, such food flavoringagents have been preferred over natural flavoring agents at least inpart due to their diminished cost and their reproducible flavorqualities. For example, natural food flavoring agents such as extracts,concentrates and the like are often subject to wide variations due tochanges in the quality, type and treatment of the raw materials. Suchvariations can be reflected in the end product and result in unfavorableflavor characteristics in said end product. Additionally, the presenceof the natural product in the ultimate food may be undesirable becauseof increased tendency to spoil. This is particularly troublesome in foodand food uses where such products as dips, soups, chips, sausages,gravies and the like are apt to be stored prior to use.

The fundamental problem in creating artificial flavor agents is that theartificial flavor to be achieved be as natural as possible. Thisgenerally proves to be a difficult task since the mechanism for flavordevelopment in many foods is not completely known. This is noticeable inproducts having sweet, cocoa butter-like, herbaceous, green, floral andanise (licorice-like) flavoring and aroma characteristics.

Reproduction of sweet, cocoa-butter-like, herbaceous, green, floral andanise flavor and aroma characteristics has been the subject of long andcontinuing searches by those engaged in the production of foodstuffs andbeverages. The severe shortage of food in many parts of the world hasgiven rise to the development of previously unused sources of proteinwhich are unpalatable. Accordingly, the need has arisen for the use offlavoring materials which will make such sources of protein palatable tohuman sensory organs.

Even more desirable is a product that can serve to substitute fordifficult-to-obtain natural perfumery oils and at the same timesubstitute for natural flavoring ingredients in both foodstuffs as wellas tobacco. Cocoa-like, sweet, floral and green aroma and tastecharacteristics in smoking tobacco both prior to and on smoking in themain stream and in the side stream are particularly desirable for usesin conjunction with smoking tobacco and smoking tobacco articles, likecigarettes, cigars and the like.

Oxygenated compounds having a bicyclopentadiene nucleus are known in theprior art and uses thereof in perfumery are also known. Thus, forexample, Kheisets and Virezub at Chem. Abstracts, 61, 8199c (Abstract ofZh. Obshch. Khim. 34 (6) 2081-4) discloses for use in perfumerycompounds having the structure: ##STR7##

The Zeinalov, et al at Chem. Abstracts, 68, 49319d, discloses thecompound having the structure: ##STR8## wherein R is methyl, n-propyl orn-butyl.

Opdyke in Chem. Abstracts, 92:11070y (Abstract of Food, Cosmet. Toxicol.1976, 14, Suppl. 889) discloses the compound having the structure:##STR9## in fragrance raw materials and its toxicological properties.

For use in perfumery, U.S. Pat. No. 3,593,745 issued on Aug. 10, 1971discloses the compound having the structure: ##STR10##

The compound having the structure: ##STR11## is disclosed in UnitedKingdom Pat. No. 815,232 issued on June 24, 1959.

Furthermore, the compound having the structure: ##STR12## has been inuse in the perfume industry for the past ten years and is known as"Cyclaprop".

German Offenlengungsschrift No. 2,642,519 published on Mar. 23, 1978 andabstracted in Chem. Abstracts, 91:56477g discloses for use in perfumerythe compounds having the structures: ##STR13## and generically thecompound having the structure: ##STR14## wherein R₇ is alkyl or alkenyl.

U.S. Pat. No. 4,123,394 issued on Oct. 31, 1978 discloses specificallythe compound having the structure: ##STR15## and generically thecompound having the structure: ##STR16## wherein R₈ is hydrogen, acyl,alkyl or alkenyl.

Arctander, "Perfume and Flavor Chemicals (Aroma Chemicals)", 1969 atmonograph 1582 discloses 3a,4,5,6,7,7a-hexahydro-4,7-methano-5-indanohaving the structure: ##STR17## and indicates it to be a semi-solidcrystalline mass or a viscous pale straw colored or almost colorlessliquid having a peculiar earthy, sweet, musky odor of moderate tenacity.Arctander indicates that "a number of adducts and derivatives have beenmade and a few have become useful in perfume chemicals" and further thatthis material has notes in common with sandalwood, oakmoss, cedarwoodand galbanum and it could be used in conjunction with certain materials.Arctander further states that this compound is stable in soap and offersa low cost material for soap, detergent and other household productfragrances and its musky character blends well with woody and amber-likenotes but leaves a floral picture out of the question. Arctander furtherstates that this material is rarely offered under its chemical name butit may enter various specialities and perfume bases as a minor componentand during the 1965-1966 period of scarcity and high prices of patchoulioil, the subject alcohol found some uses in the creation of patchoulioil substitutes. Reference is made by Arctander to U.S. Pat. No.3,271,259 issued on Sept. 6, 1966.

U.S. Pat. No. 3,271,259 issued on Sept. 6, 1966 entitled "SyntheticLavandin Oil" discloses the use in perfumery of the compound having thestructure: ##STR18## particularly in producing synthetic lavandin oil.

French Pat. No. 2,424,244 (corresponding to British PublishedApplication No. 2,019,841) discloses8-exo-hydroxymethyl-endo-tricyclodecanes useful as perfumery agents insoaps, shampoos, cosmetics and waxes wherein the fragrances range fromgreen, green grass-like, fruit-like to wood-like. The generic structureof the compounds discloses in French Pat. No. 2,424,244 (assigned to KaoSoap Company of Japan) is: ##STR19## wherein R is unsaturated C₁ -C₅alkyl, C₁ -C₅ acyl or oglycidyl and the esters are prepared from thecompound wherein R is H by means of esterification with a carboxylicacid and a mineral acid catalyst and ethers are prepared from thecompound wherein R equals H using a sodium hydride/alkyl iodide compoundand the oglycidyl ethers are prepared from allyl ethers by treatmentwith peracids.

Australian Pat. No. AU-B1-22330/77 (No. 506,675 filed on Feb. 16, 1977and the abstract for which is published in Vol. 50, No. 1 of theOfficial Journal of Patents, Trademarks and Designs of Australiadiscloses a wood polymer composite comprising a wood substrateimpregnated with a dicyclopentenyl acrylate or methacrylate polymerhaving as a repeating component: ##STR20## wherein R is hydrogen ormethyl, R' and each R" are independently hydrogen, chlorine or bromine,n is 0 or 1, and the dashed line represents a carbon-carbon single bondor a carbon-carbon double bond with the proviso that when the dashedline is a carbon-carbon double bond, n is 0, but when the dashed line isa carbon-carbon single bond, n is 1. The Australian Patent, however,does not disclose any utilities of the monomeric precursor in perfumery.

The compound having the generic structure: ##STR21## wherein Y is amoiety having a structure selected from the group consisting of:##STR22## wherein one of the dashed lines represents a carbon-carbonsingle bond and the other of the dashed lines represents a carbon-carbondouble bond; wherein R₁ and R₂ represent hydrogen or methyl with theproviso that one of R₁ and R₂ is hydrogen and the other of R₁ and R₂ ismethyl; wherein R₃ is hydrogen, C₁ -C₃ acyl, C₃ or C₄ alkyl or C₃ or C₄alkenyl; wherein R₄, R₅ and R₆ represent hydrogen or methyl with theadditional proviso that one of R₄, R₅ and R₆ is methyl and the other twoof R₄, R₅ and R₆ is hydrogen have properties which are unexpected,unobvious and advantageous insofar as organoleptic uses are concernedwhen compared with the compounds of the prior art as discussed above.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 represents the GLC profile for the reaction product producedaccording to Example I primarily containing the compound having thestructure: ##STR23##

FIG. 2 represents the NMR spectrum for the reaction product of Example Icontaining the compound having the structure: ##STR24##

FIG. 3 represents the infrared spectrum for the compound having thestructure: ##STR25## produced according to Example I.

FIG. 4 represents the GLC profile for the reaction product of Example IIcontaining primarily the compound having the structure: ##STR26##

FIG. 5 represents the NMR spectrum for the compound having thestructure: ##STR27## produced according to Example II.

FIG. 6 represents the infrared spectrum for the compound having thestructure: ##STR28## produced according to Example II.

FIG. 7 represents the GLC profile for the compounds produced accordingto Example III having the structures: ##STR29##

FIG. 8 represents the NMR spectrum for the compounds having thestructures: ##STR30## produced according to Example III.

FIG. 9 represents the infrared spectrum for the compounds having thestructures: ##STR31## produced according to Example III.

FIG. 10 represents the GLC profile for the compound having thestructure: ##STR32## produced according to Example VI.

FIG. 11 represents the NMR spectrum for the compound having thestructure: ##STR33## produced according to Example VI.

FIG. 12 represents the infrared spectrum for the compound having thestructure: ##STR34## produced according to Example VI.

FIG. 13 represents the GLC profile for the compound primarily having thestructure: ##STR35## produced according to Example VII.

FIG. 14 represents the NMR spectrum for the compound having thestructure: ##STR36## produced according to Example VII.

FIG. 15 represents the infrared spectrum for the compound having thestructure: ##STR37## produced according to Example VII.

FIG. 16 represents the GLC profile for reaction product of Example VIIIcontaining, primarily, the compound having the structure: ##STR38##

FIG. 17 represents the NMR spectrum for the reaction product of ExampleVIII containing primarily the compound having the structure: ##STR39##

FIG. 18 represents the infrared spectrum for the reaction product ofExample VIII containing, primarily, the compound having the structure:##STR40##

FIG. 19 represents the GLC profile for the reaction product producedaccording to Example IX containing, primarily, the compound having thestructure: ##STR41##

FIG. 20 represents the NMR spectrum for the reaction product of ExampleIX containing, primarily, the compound having the structure: ##STR42##

FIG. 21 represents the infrared spectrum for the reaction product ofExample IX containing, primarily, the compound having the structure:##STR43##

FIG. 22 represents the GLC profile for the reaction product of Example Xcontaining, primarily, the compound having the structure: ##STR44##

FIG. 23 represents the NMR spectrum for the reaction product of ExampleX containing, primarily, the compound having the structure: ##STR45##

FIG. 24 represents the infrared spectrum for the reaction product ofExample X containing, primarily, the compound having the structure:##STR46##

FIG. 25 represents the GLC profile for the reaction product of ExampleIX containing, primarily, the compounds having the structures: ##STR47##

FIG. 26 represents the NMR spectrum for the compound produced accordingto Example IV having the structure: ##STR48##

FIG. 27 represents the NMR spectrum for the compound produced accordingto Example IV having the structure: ##STR49##

FIG. 28 represents the NMR spectrum for the compound having thestructure: ##STR50## produced according to Example IV.

FIG. 29 represents the infrared spectrum for the compound having thestructure: ##STR51## produced according to Example IV.

FIG. 30 represents the infrared spectrum for the compound having thestructure: ##STR52## produced according to Example IV.

FIG. 31 represents the NMR spectrum for the compound produced accordingto Example XI having the structures: ##STR53##

FIG. 32 represents the GLC profile for the reaction product of ExampleXII containing the products having the structures: ##STR54##

FIG. 33 represents the NMR spectrum for fraction 5 of the distillate ofthe reaction product of Example XII containing the compounds having thestructures: ##STR55##

FIG. 34 represents the infrared spectrum for fraction 5 of thedistillation product of the reaction product of Example XII containingthe compounds having the structures: ##STR56##

FIG. 35 represents the mass spectrum for fraction 5 of the distillationproduct of the reaction product of Example XII containing the compoundshaving the structures: ##STR57##

DETAILED DESCRIPTION OF THE DRAWING

FIG. 25 is the GLC (gas liquid chromatography) profile (conditions:1/8"×10' column coated with 10% SE-30). The peak indicated with thenumeral 1 signifies the compound having the structure: ##STR58## Thepeak indicated by the numeral 2 signifies the compound having thestructure: ##STR59## The peak signified by the numeral 3 signifies thecompound having the structure: ##STR60##

The compound having the structure: ##STR61## has a strong patchouliaroma.

In FIG. 5 which represents the GLC profile for the reaction product ofExample XII, reference "4" and reference "5" represent products(ratio:20.51 for peak "4":18.60 for peak "5") and peak "6" representsthe solvent peak for the GLC run. The GLC profile was carried out usingan SE-30 column. Peak "4" and peak "5" contain the structures: ##STR62##and the structure: ##STR63## is in itself a mixture of positionalisomers and each of the structures: ##STR64## represent mixtures of"cis" and "trans" isomers or "endo" and "exo" isomers. The GLC column isa 1/4"×10' SE-30 packed column programmed at 200° C.

THE INVENTION

It has now been determined that certain substituted tricyclodecanederivatives are capable of imparting a variety of flavors and fragrancesto various consumable materials. Briefly, our invention contemplatesaugmenting or enhancing the flavors and/or fragrances of such consumablematerials by adding thereto a small but effective amount of at least onesuch substituted tricyclodecane derivatives defined according to thegeneric structure: ##STR65## wherein Y is a moiety having a structureselected from the group consisting of: ##STR66## wherein one of thedashed lines represents a carbon-carbon single bond and the other of thedashed lines represents a carbon-carbon double bond; wherein R₁ and R₂represent hydrogen or methyl with the proviso that one of R₁ and R₂ ishydrogen and the other of R₁ and R₂ is methyl; wherein R₃ is hydrogen,C₁ -C₃ acyl, C₃ or C₄ alkyl or C₃ or C₄ alkenyl; wherein R₄, R₅ and R₆represent hydrogen or methyl with the additional proviso that one of R₄,R₅ and R₆ is methyl and the other two of R₄, R₅ and R₆ is hydrogen andflavoring (e.g., for foodstuffs, chewing gum, chewing tobaccos,medicinal products and smoking tobacco) and fragrance compositions(e.g., perfume compositions and compositions for augmenting or enhancingthe aroma of perfumed articles, such as solid or liquid anionic,cationoc, nonionic, zwitterionic detergents or fabric softeners orcosmetic powders) containing such substituted tricyclodecanederivatives. The invention also contemplates novel processes forproducing such compounds.

The substituted tricyclodecane derivatives produced according to theprocesses of our invention which are used in practicing that part of ourinvention concerning flavoring and fragrance compositions are actuallyracemic mixtures rather than individual stereoisomers, such as is thecase concerning isomers of patchouli alcohol isomers which are obtainedfrom patchouli oil.

The substituted tricyclodecane derivatives of our invention insofar astheir fragrance profiles are concerned have green, floral, woody,patchouli-like, musty-camphoraceous, rosey, woody, anisic, ionone-like,fruity (banana), spicey (cinnamic), bitter sweet, milky,petitgrain-like, lavender, bergamot-like, fatty and minty aromas withspicey, green, basil, raspberry-like, sweatey, pith-like, pumpkin-likeand creamy undertones and fruity/berry intense aromas on dry out.

Insofar as their flavor uses are concerned, (e.g., foodstuffs, chewinggums, medicinal products and chewing tobaccos), the substitutedtricyclodecane derivatives of our invention have sweet, cocoabutter-like, herbaceous, green, floral, and anise aroma profiles andsweet, cocoa butter-like, herbaceous, green, floral and anise flavorprofiles.

Insofar as smoking tobacco flavors are concerned, the substitutedtricyclodecane derivatives of our invention have cocoa-like, sweet,floral and green aroma profiles prior to smoking the sweet, floral andaromatic aroma and taste nuances on smoking in both the main stream andthe side stream.

The following table sets forth the structure and organoleptic propertyprofiles for specific compounds according to the Examples listed hereinand located infra:

                                      TABLE I                                     __________________________________________________________________________                          Food    Tobacco                                                      Fragrance                                                                              Flavor  Flavor                                          Structure    Profile  Profile Profile                                         __________________________________________________________________________     ##STR67##   A strong maple aroma with pump- kin-like and slightly spicy                   under- tones.    A sweet, fruity, citrusy aroma and taste                                      prior to and on smoking in both the main                                      stream and the side stream.                      ##STR68##   A fruity, anisic aroma with a rasp- berry under- tone; on                     dry- out, fruity and berry- like.                                                      A sweet, cocoa butter-like, herbaceous and green                              aroma and flavor pro- file at 0.2 ppm and at 1 ppm,                           erbaceous and green notes domin- ate over the                                 cocoa- butter character.                                                              A sweet, woody, spicy, herbac- eous aroma                                     and taste both prior to and on smoking in                                     the main stream and side stream.                 ##STR69##   A woody, resinous, camphoraceous patchouli- like aroma                        reminiscent of patchouli alcohol; with oakmoss undertones                     then green, and woody and floral and rosey topnotes.                                   A floral, fruity, cit- ronellol-like and patchouli                            aroma char- acteristic with a floral, fruity, cit-                            ronellol-like patchouli and fresh walnut flavor                               char- acteristic at 2 ppm.                                                            A sweet, herbaceous, spicy,                                                   hay- clover-like and woody aroma and taste                                    profile both prior to and on smoking in the                                   main stream and the side stream.                 ##STR70##   A fatty, slightly minty and camphoraceous aroma with                          pith-like and pumpkin nuances as well as woody and piney                      under- tones.                                                                          A floral, herbaceous, citrus-like, fruity and                                 patchouli- like aroma and taste and flavor profile                            at 5 ppm.                                                                             A sweet, creamy and buttery aroma and taste                                   oth prior to and on smok-  ing in the main                                    stream and in the  side stream.                  ##STR71##   A green, fruity, creamy, rhubarb stem- like and banana-like                   aroma.   A green, fruity, pear- like, cocoa butter-like                                aroma and flavor pro- file causing it to be useful                            in pea flavor and cocoa butter flavor                                         for- mulations at 1 ppm.                                                              A sweet, fruity, plum- like, fatty,                                           cucumber-like aroma and taste both prior to                                   and on smoking in the main stream and in                                      the side stream.                                 ##STR72##   A strong, herbaceous aroma with an oily and spicey, green,                    basil under- tone.                                                                     A sweet, floral, anise- like, green and herbac-                               eous aroma and flavor profile at 1                                                    A cocoa-like, sweet, floral and green aroma                                   prior to smoking and a sweet, floral and                                      green aroma on smoking in the main stream                                     and in the side stream.                          ##STR73##   A low keyed fruity (banana), spicey (cin- namic), green                       aroma with sweaty and creamy under- tones.                                             A green, waxy, cocoa- butter-like aroma pro-  file                            with a green, waxy, cocoa powder and bitter flavor                            pro- file at 2 ppm.                                                                   A sweet, floral, carnation, creamy aroma                                      and taste prior to smoking and a green,                                       floral aroma and taste on smoking in the                                      main stream and in the side stream.              ##STR74##   A bitter, sweet, herbal, petitgrain- like, lavender and                       bergamot aroma pro- file with floral under- tones.                                     A green, floral aroma character- istic with bitter                            flavor character- istics at 0.1 ppm.                                                  A sweet, green, cucumber, melon, pea- like                                    aroma and taste both prior to and on                                          smoking in the main stream and the side                                       stream.                                          ##STR75##   A minty, spicey, fruity aroma with caryophyll- ene-like,                      cedarwood and sandal- wood under- tones becoming borneol-                     woody-like on a dry- out.                                                              A minty, cooling, camphorac- eous, pat- chouli-like                           roma and flavor pro- file causing it to be useful                             in oral hygiene flavors, mint flavors and pepper-                             mint flavors at 2 ppm.                                                                A earthy, grapefruit peel-like, albedo,                                       cam- phoraceous aroma and taste both prior                                    to and on smoking in the main stream and in                                   he side stream.                                  ##STR76##   A fruity (apple), anisic-like aroma with dry, hay- like and                   berry-like undertones.                                                                 A green, waxy, cocoa- butter-like aroma and flavor                            character with addit- ional bitter flavor nuances                             at 1 ppm.                                                                             A sweet, woody, camphoraceous, spicey aroma                                   nd taste profile both prior to and on                                         smoking in the main stream and in the side                                    stream.                                         __________________________________________________________________________

The substituted tricyclodecane derivatives produced according to theprocess of our invention which are used in practicing that part of ourinvention concerning flavor and fragrance compositions may be mixturesof isomers or they may be substantially pure forms of exo or endoisomers or specific stereoisomers such as the case concerning isomers ofpatchouli alcohol which are obtained from patchouli oil.

The substituted tricyclodecane derivatives prepared according to ourinvention can be obtained by reacting either mixtures or specificisomers of dimethyl cyclopentadiene and these isomers have thestructures: ##STR77##

The compounds having the structures: ##STR78## may be represented inadmixture by the structural representation: ##STR79##

These materials may be prepared by dimerizing one or two or a mixture ofall three of the methyl cyclopentadiene isomers having the structures:##STR80## In addition, other isomers of the dimethylcyclopentadienestructure exist.

The ester derivatives, e.g., the formate, acetate and propionatederivatives of dimethylcyclopentadiene of our invention having thestructures: ##STR81## may be prepared by reacting one or more of theisomers of dimethylcyclopentadiene as set forth above with anappropriate alkanoic acid or mixture of alkanoic acids in the presenceof a protonic acid or a Lewis acid. Examples of protonic acids useful inthis reaction are sulfuric acid, phosphoric acid, para toluene sulfonicacid, methane sulfonic acid and acid clays, and acid ion exchangeresins. Examples of Lewis acids which may be used are borontriflouride,borontriflouride etherate, zinc chloride and stannic chloride.

The reaction temperature may vary from about 0° C. up to about 50° C.with a reaction temperature of approximately 10° C. being preferred andthe resulting yield is from 25 up to 50% by weight of the theoreticalyield based on the amount of methyl cyclopentadiene dimer reactantpresent.

The concentration of acid, whether it be Lewis acid or protonic acidcatalyst in the reaction mass, may vary from 0.01% up to 1 mole percentbased on the weight of the reaction mass. The mole ratio of methylcyclopentadiene dimer:carboxylic acid may vary from about 1:1 up toabout 1:3 moles methyl cyclopentadiene dimer:carboxylic acid.

The resulting esters may also be prepared using esterification reagentsother than alkyl carboxylic acids, for example, alkanoic acid anhydridesand mixed alkanoic acid anhydrides, such as, acetic anhydride, propionicanhydride and mixed acetic-propionic anhydride. In the alternative,other esterification reagents may be used, such as acyl halides, forexample, acetyl chloride, acetyl bromide, propionyl chloride andpropionyl bromide. When acylating agents, such as alkanoic acidanhydrides and acyl halides are used, the mole ratio of dimethylbicyclopentadiene dimer:esterifying reagent preferably is about 1:1.

The alcohol derivatives of the substituted tricyclodecane derivatives ofour invention having the structures: ##STR82## are prepared byhydrolyzing the esters prepared as indicated above. The hydrolysis takesplace in the presence of a strong alkali metal hydroxide, such as 10 upto 50% by weight sodium hydroxide. It is preferred that from 1 up to 2moles of sodium hydroxide be used per mole of ester derivative. Thehydrolysis preferably also takes place from about 40° C. up to reflux,usually about 100°-120° C. as a maximum.

Instead of carrying out the reaction in two steps; first forming theester and then hydrolyzing the ester to form the alcohol using thedimethyl bicyclopentadiene derivative as a starting reactant, the entirereaction can be done using one reactor without isolation of the ester;and this one reactor reaction preferably is carried out using theformate ester as an intermediate. In summary, the reaction sequence isillustrated by the following two reactions: ##STR83## wherein one of R₁or R₂ is methyl and the other of R₁ or R₂ is hydrogen and wherein one ofR₄, R₅ and R₆ is methyl and the other two of R₄, R₅ and R₆ is hydrogen;wherein R₃ ' is C₁ -C₃ acyl and wherein M represents alkali metal, suchas sodium, potassium and lithium, wherein one of the dashed linesrepresents a carbon-carbon single bond and the other of the dashed linesrepresents a carbon-carbon double bond.

The reaction to form the ether derivative of the methyl cyclopentadieneof our invention according to the reaction: ##STR84## wherein R₃ 'represents C₂ -C₄ alkyl or C₃ -C₄ alkenyl is carried out underconditions similar to those for preparation of the ester with theexception that, in general, the temperature of reaction is somewhathigher. The reaction is carried out between a C₂ -C₄ alkanol or a C₃ orC₄ alkenol and one or more of the dimethyl bicyclopentadiene derivativesas enumerated above. It is preferred to use from about 1 up to 3 molesof alkanol or alkenol per mole of dimethyl dicyclopentadiene dimer. Itis preferred that the catalyst be either a Lewis acid, such as borontrifluoride, boron trifluoride etherate, zinc chloride or stannicchloride or a protonic acid, such as sulfuric acid, para toluenesulfonic acid or phosphoric acid. It is further preferred that thereaction temperature be from about 25° C. up to reflux temperature, withreflux temperature being between about 100° and 125° C.

The ketone derivative of the dimethyl dicyclopentadiene dimer of ourinvention having the structures: ##STR85## are prepared by oxidation ofthe corresponding alcohols using oxidizing agents, such as copperchromite or Jones reagents. The reaction sequence is illustrated thusly:##STR86## Also useful is sodium dichromate, Jones reagent or CrO₃ thelike. The reaction that takes place is a chemical oxidation whereinequivalent quantities of oxidizing agent, e.g., sodium dichromate andalcohol are utilized. When copper chromite is used, the reaction is inthe nature of a catalytic dehydrogenation. Thus, a catalytic quantity ofcopper chromite is all that is necessary. The reaction when carried outusing catalytic dehydrogenation is preferably carried out at atemperature of between 180° and 220° C. at atmospheric pressure. Whenusing the oxidizing reaction and using such oxidizing reagents as sodiumdichromate or chromium trioxide, the reaction temperature is preferablyin the range of from about 20° C. up to about 80° C. with the use of asolvent being preferred, e.g., toluene or methylene dichloride.Pyridinium chlorochromate may also be used as an oxidizing agent withthe temperature of reaction being in the range of between about 25° C.and about 100° C.

In summary, the reaction of the hydroxy derivative of the dimethylbicyclopentadiene to the keto derivative of the dimethylbicyclopentadiene derivative of our invention is illustrated accordingto the reaction: ##STR87## wherein one of R₁ or R₂ is methyl and theother of R₁ or R₂ is hydrogen; and wherein one of R₄, R₅ and R₆ ismethyl and the other two of R₄, R₅ and R₆ are hydrogen, wherein one ofthe dashed lines represents a carbon-carbon single bond and the other ofthe dashed lines represents a carbon-carbon double bond.

In producing the compounds having the structures: ##STR88## compoundshaving the structures: ##STR89## or mixtures thereof are preferablyreduced using a reducing agent, such as hydrogen under pressure in thepresence of a hydrogenation catalyst, such as Raney nickel, andsupported palladium or platinum on carbon or calcium carbonate (e.g., a"Lindlar" catalyst of 5% palladium on calcium carbonate). By the sametoken, ethers and esters may also be hydrogenated whereby the doublebond on the dimethyl bicyclopentadiene derivative is reduced to acarbon-carbon single bond according to the reaction: ##STR90## whereinR₃ represents hydrogen, C₃ or C₄ alkenol or C₂ -C₄ alkyl or C₁ -C₃ acyl;one of R₁ or R₂ is methyl and the other of R₁ or R₂ is hydrogen; and oneof R₄, R₅ and R₆ is methyl and the other two of R₄, R₅ and R₆ representshydrogen; wherein one of the dashed lines represents a carbon-carbonsingle bond and the other of the dashed lines represents a carbon-carbondouble bond. When R₃ is alkenyl, the hydrogenation reaction will producea mixture of alkyl and alkenyl ethers, the proportion of alkyl ether inthe mixture being a function of the extent (time, pressure andtemperature) of hydrogenation carried out. A long period of time ofhydrogenation coupled with high pressure and high temperature will yieldtotal elimination of the carbon-carbon double bonds in the moleculethereby yielding alkyl ethers of dimethyl bicyclopentane derivatives,either in pure form or in admixture themselves depending upon the natureof the dimethyl bicyclopentadiene starting reactant used. The range ofreaction temperature may vary from about 10° C. up to about 50° C. witha preferred reaction pressure of from about 25 psig up to 300 psig. Itis preferred that the hydrogenation reaction be carried out in thepresence of an inert solvent, such as isopropyl alcohol, ethyl alcohol,methyl alcohol or n-butanol. When such a solvent is used, it ispreferred that the ratio of the dimethyl bicyclopentadienederivative:solvent (weight:weight) be between about 1:1 and 3:1 with apreferred ratio being 2.5:1.

In producing carboalkoxy esters (e.g., "carbonates" of the dimethylbicyclopentadiene derivatives of our invention having the structures:##STR91## the starting materials are the hydroxyl derivatives of thedimethyl bicyclopentadiene derivatives of our invention having thestructures: ##STR92## These compounds may either first be reacted withsuch materials as methyl chloroformate to form the methyl carbonatederivatives having the structures: ##STR93## in a 1:1 mole ratio ofreactants using ambient temperature and pressure or the reaction (inorder to effect a higher yield . . . quantitative yields) may be carriedout by first reacting the hydroxyl derivatives of the dimethylbicyclopentadiene derivatives of our invention having the structures:##STR94## with an alkali metal hydride, such as lithium hydride therebyforming the alkali metal salts of the dimethyl bicyclopentadienederivatives of our invention having the structures: ##STR95## wherein Mis sodium, potassium or lithium. These organometallic derivatives may inadmixture or individually be reacted with dialkyl carbonate such asdimethyl carbonate thereby producing the desired carbonate derivativesof the dimethyl bicyclopentadienes of our invention according to thereaction: ##STR96##

The temperature range most preferred for the foregoing reaction whenreacting the alkali metal hydride with the alcohol derivative of thedimethyl bicyclopentadiene is from about 40° C. up to about 70° C. andit is most preferred to carry out the reaction in an inert cosolvent,such as toluene or xylene. After the reaction is completed, the secondreaction with the dialkyl carbonate and the organometallic derivativeshould take place at reflux temperature in the same cosolvent as used inthe first reaction with the alkali metal hydride. Thus, for example, ifthe cosolvent is toluene, the reaction should take place at about refluxor between the temperatures of about 90° C. and about 115° C. The periodof time necessary for the reaction to go to completion is between about2 and about 5 hours. The reaction pressure is preferably atmospheric butsuper atmospheric pressures may be utilized without any resultantdecrease in the yield of desired reaction product.

At the end of each of the foregoing reactions, the reaction product may,if desired, be separated from the resultant reaction mass as byfractional distillation or preparative GLC (vapor phase chromatography).However, if the desired reaction product as above is to be utilized as areaction intermediate, the necessity of careful rectification of thereaction product in order to achieve odor acceptable substances orflavor acceptable substances is not necessary since the resultantreaction product will be further reacted.

It will be appreciated from the present disclosure that the substitutedtricyclodecane derivative according to the present invention can be usedto alter, vary, fortify, modify, enhance or otherwise improve the flavorof a wide variety of materials which are ingested, consumed or otherwiseorganoleptically sensed.

The terms "alter" and "modify" in their various forms will be understoodherein to mean the supplying or imparting of a flavor character or noteto an otherwise bland, relatively tasteless substance, or augmenting anexisting flavor characteristic where the natural flavor is deficient insome regard or supplementing the existing flavor impression to modifythe organoleptic character.

The term "enhance" is intended herein to mean the intensification (byuse of the substituted tricyclodecane derivative of our invention) of aflavor or aroma note or nuance in a tobacco flavor or foodstuff orperfume composition or a perfumed article without changing the qualityof said note or nuance.

A "flavoring composition" is taken to mean one which contributes a partof the overall flavor impression by supplementing or fortifying anatural or artificial flavor in a material or one which suppliessubstantially all the flavor and/or aroma character to a consumablearticle.

The term "foodstuff" as used herein includes both solid and liquidingestible materials for man or animals, which materials usually do, butneed not, have nutritional value. Thus, foodstuffs includes meats,gravies, soups, convenience foods, malt, alcoholic, and other beverages,milk and dairy products, seafoods including fish, crustaceans, mollusks,and the like, candies, vegetables, cereals, soft drinks, snacks, dog andcat food, other veterinary products, and the like.

The substituted tricyclodecane derivatives of our invention are also auseful tobacco flavorant and flavor enhancer.

The term "tobacco" will be understood herein to mean natural productssuch as, for example, burley, Turkish tobacco, Maryland tobacco,flue-cured tobacco and the like including tobacco-like or tobacco-basedproducts such as reconstituted or homogenized leaf and the like, as wellas tobacco substitutes intended to replace natural tobacco, such aslettuce and cabbage leaves and the like. The tobaccos and tobaccoproducts in which the substituted tricyclodecane derivatives of ourinvention are useful include those designed or used for smoking such asin cigarette, cigar and pipe tobacco, as well as products such as snuff,chewing tobacco, and the like.

When the substituted tricyclodecane derivatives of this invention areused in a flavoring composition, they can be combined with conventionalflavoring materials or adjuvants. Such co-ingredients or flavoringadjuvants are well known in the art for such use and have beenextensively described in the literature. Requirements of such adjuvantmaterials are: (1) that they be non-reactive with the substitutedtricyclodecane derivatives of our invention; (2) that they beorganoleptically compatible with the substituted tricyclodecanederivatives of our invention whereby the flavor of the ultimateconsumable material to which the substituted tricyclodecane derivativesare added is not detrimentally affected by the use of the adjuvant and(3) that they be ingestibly acceptable, and thus non-toxic or nototherwise non-deleterious. Apart from these requirements, conventionalmaterials can be used and broadly include other flavor materials,vehicles, stabilizers, thickeners, surface active agents, conditioners,and flavor intensifiers.

Such conventional flavoring materials include saturated fatty acids,unsaturated fatty acids and amino acids; alcohols, including primary andsecondary alcohols, esters; carbonyl compounds including ketones andaldehydes; lactones; other cyclic organic materials including benzenederivatives, alicyclic compounds, heterocyclics such as furans,pyridines, pyrazines and the like; sulfur-containing materials includingthiols, sulfides, disulfides and the like; proteins; lipids,carbohydrates; so-called flavor potentiators such as monosodiumglutamate, guanylates, and inosinates; natural flavoring materials suchas cocoa, vanilla and caramel; essential oils and extracts such as aniseoil; clove oil; and the like; and artificial flavoring materials such asvanillin; and the like.

Specific preferred flavor adjuvants are as follows:

Ethyl-2-methyl butyrate;

Vanillin;

Butyl valerate;

2,3-Diethyl pyrazine;

Methyl cyclopentenolone;

Benzaldehyde;

Valerian Oil Indian; and

Propylene glycol

When used in perfumery, in order to alter, modify or enhance the aromaof perfume compositions, or perfumed articles the substitutedtricyclodecane derivatives of our invention can be used to contributepatchouli-like, peppery, woody, fruity and camphoraceous aromas. As anolfactory agent, the substituted tricyclodecane derivatives of thisinvention can be formulated into or used as a component of a "perfumecomposition".

The term perfume composition is used herein to mean a mixture of organiccompounds, including, for example, alcohols, aldehydes, ketones,nitriles, esters, and frequently hydrocarbons which are admixed so thatthe combined odors of the individual components produce a pleasant ordesired fragrance. Such perfume compositions usually contain (a) themain note of the "bouquet" or foundation stone of the composition; (b)modifiers which round off and accompany the main note; (c) fixativeswhich include odorous substances which lend a particular note to theperfume throughout all stages of evaporation, and substances whichretard evaporation; and (d) topnotes which are usually low boiling freshsmelling materials.

In perfume compositions, the individual component will contribute itsparticular olfactory characteristics but the overall effect of theperfume composition will be the sum of the effect of each ingredient.Thus, the substituted tricyclodecane derivatives of this invention canbe used to alter, modify or enhance the aroma characteristics of aperfume composition, for example, by highlighting or moderating theolfactory reaction contributed by another ingredient in the composition.

The amount of the substituted tricyclodecane derivatives of thisinvention which will be effective in perfume compositions depends onmany factors, including the other ingredients, their amounts and theeffects which are desired. It has been found that perfume compositionscontaining as little as 1 percent of the substituted tricyclodecanederivatives of this invention, or even less, can be used to impart apatchouli scent with peppery, woody, fruity and camphoraceous notes tosoaps, cosmetics, and other products. The amount employed can range upto 50% or higher and will depend on considerations of cost, nature ofthe end product, the effect desired on the finished product andparticular fragrance sought.

The substituted tricyclodecane derivatives of this invention can be usedalone or in a perfume composition as an olfactory component indetergents, and soaps, space odorants and deodorants; perfumes;colognes; toilet waters; bath salts; hair preparations such as lacquers,brilliantines, pomades, and shampoos; cosmetic preparations such ascreams, deodorants, hand lotions, and sun screens; powders such astalcs, dusting powders, face powder, and the like. When used as anolfactory component of a perfumed article, as little as 0.01 percent ofone or more of the substituted tricyclodecane derivatives will sufficeto impart a patchouli aroma with peppery, woody, fruity andcamphoraceous notes. Generally, no more than 0.5 percent is required.

In addition, the perfume composition can contain a vehicle or carrierfor the substituted tricyclodecane derivatives alone or with otheringredients. The vehicle can be a liquid such as an alcohol such asethanol, a glycol such as propylene glycol, or the like. The carrier canbe an absorbent solid such as a gum or components for encapsulating thecomposition.

The following examples are given to illustrate embodiments of theinvention as it is presently preferred to practice it. It will beunderstood that these examples are illustrative, and the invention isnot to be considered as restricted thereto except as indicated in theappended claims.

EXAMPLE I PREPARATION OF HEXAHYDRO-5-FORMYLOXY-2 (AND3),4-DIMETHYL-4,7-METHANOINDENE ##STR97##

Methyl cyclopentadiene dimer (1072 grams) is slowly added over atwo-hour period to a stirred solution of 95% formic acid (480 grams) andsulfuric acid (50 grams) at 6° to 10° C. The mass is stirred for twohours at 5° C. and then poured into two liters of water. The organiclayer is washed twice with water and distilled through a short column toafford 460 grams of hexahydro-5-formyloxy-2 (and3),4-dimethyl-4,7-methanoindene (b.p. 100° to 135° C. at 33 mm Hg.pressure).

FIG. 1 is the GLC profile of the product (200° C. isothermal; 1/4"×10'10% SE-30 packed column).

FIG. 2 shows the NMR spectrum of hexahydro-5-formyloxy-2 (and3),4-dimethyl-4,7-methanoindene.

FIG. 3 shows the IR spectrum of hexahydro-5-formyloxy-2 (and3),4-dimethyl-4,7-methanoindene.

EXAMPLE II PREPARATION OF HEXAHYDRO-5-ACETOXY-2 (AND3),4-DIMETHYL-4,7-METHANOINDENE ##STR98##

Methylcyclopentadiene dimer (640 grams) is added to a stirred solutionof acetic acid (300 grams), toluene (400 ml), and boron triflourideetherate (80 grams) at 45° C. over a two-hour period. The mass isstirred at 45° C. for one hour and then poured into one liter of waterand 500 ml of toluene. The organic layer is washed two times with water,one time with 10% sodium bicarbonate, and one time with water again. Theorganic layer is rushed over and the crude product is fractionallydistilled through a 11/2"×12' packed column to afford 373 grams ofhexahydro-5-acetoxy-2 (and 3),4-dimethyl-4,7-methanoindene (b.p. 94° C.at 1.7 mm Hg. pressure).

FIG. 4 shows the GLC trace of hexahydro-5-acetoxy-2 (and3),4-dimethyl-4,7-methanoindene (200° C. isothermal 1/4"×10' 10% SE-30packed column).

FIG. 5 shows the NMR spectrum of hexahydro-5-acetoxy-2 (and3),4-dimethyl-4,7-methanoindene.

FIG. 6 shows the IR spectrum of hexahydro-5-acetoxy-2 (and3),4-dimethyl-4,7-methanoindene.

EXAMPLE III PREPARATION OF HEXAHYDRO-5-HYDROXY-2 (AND3),4-DIMETHYL-4,7-METHANOINDENE ##STR99##

A solution of 400 grams of hexahydro-5-formyloxy-2 (and3),4-dimethyl-4,7-methanoindene, 480 grams of 50% sodium hydroxide, 400ml of toluene, and 100 ml of methanol are heated at reflux for twohours. The mass is cooled. The organic layer is separated and washed twotimes with water. Distillation through a 11/2"×12' packed column affords365 grams of product (b.p. 88°-106° C. at 3 mm Hg. pressure).

FIG. 7 shows the GLC trace of hexahydro-5-hydroxy-2 (and3),4-dimethyl-4,7-methanoindene (220° C. isothermal, 1/4"×10' 10% SE-30packed column).

FIG. 8 shows the NMR spectrum of hexahydro-5-hydroxy-2 (and3),4-dimethyl-4,7-methanoindene.

FIG. 9 shows the IR spectrum of hexahydro-5-hydroxy-2 (and3),4-dimethyl-4,7-methanoindene.

EXAMPLE IV PREPARATION OF HEXAHYDRO-5-HYDROXY-2 (AND3),4-DIMETHYL-4,7-METHANOINDENE ##STR100##

Methyl cyclopentadiene dimer (6480 grams) is slowly added over a fivehour period to a stirred solution of 95% formic acid (2905 grams) andsulfuric acid (294 grams) at 6° to 10° C. The mass is stirred 30 minutesat 5° C. and then poured into 3 liters of 10% salt solution withstirring. The organic layer is added to a stirred solution of 4800 gramsof 50% sodium hydroxide solution and 1 liter of methanol. The mixture isheated at reflux for 3 hours, whereupon it is poured into 3 liters ofsalt solution and 1 liter of toluene. The organic layer is rushed overand distilled to afford 3600 grams of product (b.p. 88°-100° C., 3 mmHg. pressure).

EXAMPLE V PREPARATION OF HEXAHYDRO-5-HYDROXY-2 (AND3),4-DIMETHYL-4,7-METHANOINDENE ##STR101##

A solution of 474 grams of hexahydro-5-acetoxy-2-(and3),4-dimethyl-4,7-methanoindene, 240 grams of 50% sodium hydroxidesolution, 15 grams of cetyl trimethyl ammonium chloride, and 300 ml oftoluene is heated at reflux for 6 hours. The reaction mass is pouredinto one liter of water. The organic layer is washed once with water andrushed over. Fractional distillation through a 11/2"×12' packed columnaffords 339 grams of hexahydro-5-hydroxy-2 (and3),4-dimethyl-4,7-methanoindene (b.p. 75°-80° C., 1.4 mm Hg. pressure).

EXAMPLE VI PREPARATION OF 3a,6,7,7a-TETRAHYDRO-2 (AND3),4-DIMETHYL-4,7-METHANOINDEN-5(4H)-ONE ##STR102##

A mixture of 500 grams of hexahydro-2 (and3),4-dimethyl-4,7-methanoindene, 20 grams of Primol^(R), and 10 grams ofcopper chromite are heated slowly to 220°-240° C. Hydrogen gas isevolved over a period of 4 hours. The reaction mass is cooled and theorganic mass distilled through a 11/2"×12' packed column to afford 460grams of 3a,6,7,7a-tetrahydro-2 (and3),4-dimethyl-4,7-methanoindene-5(4H)-one (b.p. 85° C. at 1.1 mm Hg.pressure). The material solidifies upon standing.

FIG. 10 shows the GLC profile of 3a,6,7,7a-tetrahydro-2 (and3),4-dimethyl-4,7-methanoinden-5(4H)-one.

FIG. 11 shows the mass spectrum of 3a,6,7,7a-tetrahydro-2 (and3),4-dimethyl-4,7-methanoinden-5(4H)-one.

FIG. 12 shows the IR spectrum of 3a,6,7,7a-tetrahydro-2 (and3),4-dimethyl-4,7-methanoinden-4-(4H)-one.

EXAMPLE VII PREPARATION OF HEXAHYDRO-2 (AND3),4-DIMETHYL-5-PROPIONOXY-4,7-METHANOINDENE ##STR103##

Methylcyclopentadiene dimer (320 grams) is added to a solution of borontrifluoride etherate (20 ml), propionic acid (163 grams) and toluene(200 ml) at 30° C. over a 90-minute period. The mass is stirred threehours at 30° C. and then poured into 500 ml of salt solution. Theorganic layer is washed with water and then washed with dilute sodiumbicarbonate solution. The organic mass is rushed over and fractionallydistilled through a 11/2"×1' packed column to afford 285 grams ofhexahydro-2 (and 3),4-dimethyl-5-propionoxy-4,7-methanoindene (b.p. 100°C. at 1 mm Hg. pressure).

FIG. 13 represents the GLC profile of the crude reaction productcontaining hexahydro-2 (and 3),4-dimethyl-5-propionoxy-4,7-methanoindene(200° C. isothermal, 1/4'×10' 10% SE-30 packed column).

FIG. 14 shows the NMR spectrum of hexahydro-2 (and3),4-dimethyl-5-propionoxy-4,7-methanoindene.

FIG. 15 shows the IR spectrum of hexahydro-2 (and3),4-dimethyl-5-propionoxy-4,7-methanoindene.

EXAMPLE VIII PREPARATION OF HEXAHYDRO-5-ALLYLOXY-2 (AND3),4-DIMETHYL-4,7-METHANOINDENE ##STR104##

Methyl cyclopentadiene dimer (320 grams) is added to a solution of borontrifluoride etherate (40 grams), allyl alcohol (174 grams) and toluene(200 ml) at 60° C. over a one-hour period. The mass is stirred at 60° C.for 90 minutes and poured into 500 ml of water. The organic layer iswashed twice with water and then rushed over. Fractional distillationthrough a 11/2"×12' packed column affords 375 grams ofhexahydro-5-allyloxy-2 (and 3),4-dimethyl-4,7-methanoindene (b.p. 84° C.at 1 mm Hg. pressure).

FIG. 16 represents the GLC profile of hexahydro-5-allyloxy-2 (and3),4-dimethyl-4,7-methanoindene (200° C. isothermal, 1/4"×10' 10% SE-30packed column).

FIG. 17 shows the NMR spectrum of hexahydro-5-allyloxy-2 (and3),4-dimethyl-4,7-methanoindene.

FIG. 18 shows the IR spectrum of hexahydro-5-allyloxy-2 (and3),4-dimethyl-4,7-methanoindene.

EXAMPLE IX PREPARATION OF HEXAHYDRO-5-BUTYLOXY-2 (AND3),4-DIMETHYL-4,7-METHANOINDENE ##STR105##

A solution of 352 grams of hexahydro-5-hydroxy-2 (and3),4-dimethyl-4,7-methanoindene in 300 ml of toluene is dropwise addedat 80° C. over a 90-minute period to a stirred slurry of 96 grams of 53%sodium hydride in 700 ml of toluene. Hydrogen gas evolves as theaddition proceeds. The reaction mass is heated at reflux for one hourafter the addition is completed. The mass is cooled to 75° C. A mixtureof 1-bromobutane (304 grams) and 10 grams of cetyl trimethyl ammoniumchloride are added over a one-hour period. The mass is heated at 75° C.for 5 hours. The mixture is cooled and poured into 1 liter of water. Theorganic layer is washed twice and rushed over. Fractional distillationthrough a 11/2"×12' packed column affords 384 grams ofhexahydro-5-butyloxy-2 (and 3),4-dimethyl-4,7-methanoindene (b.p. 105°C. at 1.6 mm Hg. pressure).

FIG. 19 represents the GLC profile of hexahydro-5-butyloxy-2 (and3),4-dimethyl-4,7-methanoindene (200° C. isothermal, 1/2"×10' 10% SE-30packed column).

FIG. 20 represents the NMR spectrum of hexahydro-5-butyloxy-2 (and3),4-dimethyl-4,7-methanoindene.

FIG. 21 represents the IR spectrum of hexahydro-5-butyloxy-2 (and3),4-dimethyl-4,7-methanoindene.

EXAMPLE X PREPARATION OF HEXAHYDRO-5-ISOPROPOXY-2 (AND3),4-DIMETHYL-4,7-METHANOINDENE ##STR106##

Methyl cyclopentadiene dimer (320 grams) is added to a stirred solutionof boron trifluoride etherate (20 ml), isopropanol (132 grams) andtoluene (200 grams) at 60° C. over a 1-hour period. The mass is stirredat 60° C. for three hours and then poured into 1 liter of saturated saltsolution. The organic layer is washed twice with water and then rushedover. Fractional distillation affords 222 grams hexahydro-5-isopropoxy-2(and 3),4-dimethyl-4,7-methanoindene (b.p. 80° C. at 0.7 mm Hg.pressure).

FIG. 22 represents the GLC profile of the crude reaction productcontaining hexahydro-5-isopropoxy-2 (and3),4-dimethyl-4,7-methanoindene.

FIG. 23 represents the NMR spectrum of hexahydro-5-isopropoxy-2 (and3),4-dimethyl-4,7-methanoindene.

FIG. 24 represents the IR spectrum of hexahydro-5-isopropoxy-2 (and3),4-dimethyl-4,7-methanoindene.

EXAMPLE XI PREPARATION OF 5-HYDROXY-2 (AND3),4-DIMETHYL-4,7-METHANOINDENE ##STR107##

A solution of 500 grams of hexahydro5-hydroxy-2 (and3),4-dimethyl-4,7-methanoindene and 200 grams of isopropanol arehydrogenated at 50 psi and 25° C. over 2 grams of 10% palladium oncharcoal. After the uptake of 98% of the calculated hydrogen, thesolution is filtered and distilled to afford 482 grams ofhexahydro-5-hydroxy-2 (and 3),4-dimethyl-4,7-methanoindene (b.p. 99° C.at 2 mm. Hg. pressure).

FIG. 31 represents the NMR spectrum of 5-hydroxy-2 (and3),4-dimethyl-4,7-methanoindene.

EXAMPLE XII PREPARATION OF HEXAHYDRO-2 (AND3),4-DIMETHYL-4,7-METHANOINDEN-5-METHYLCARBONATE ##STR108##

A solution of 356 grams of 5-hydroxy hexahydro-2 (and3),4-dimethyl-4,7-methanoindene in 500 ml of toluene is added dropwiseto a stirred slurry of lithium hydride (24 grams) and 500 ml toluene at50° C. over a 90-minute period. Hydrogen is eliminated as the additionproceeds. The reaction mass is stirred at 50° C. for one hour whereupon270 grams of dimethyl carbonate are added over a 30-minute period. Theresulting mass is heated to reflux (95° C.) for three hours. 300 ml ofsolvent are distilled off at atmospheric pressure. The organic solutionis cooled and washed two times with water and distilled to afford 187grams of hexahydro-2 (and 3),4-dimethyl-4,7-methanoinden-5-methylcarbonate (b.p. 115°L C., 1.8 mm. Hg. pressure). The material solidifiesupon standing.

FIG. 32 represents the GLC profile for the above reaction product.

FIG. 33 represents the NMR spectrum for fraction 5 of the distillate.

FIG. 34 represents the IR spectrum for fraction 5 of the distillate.

FIG. 35 represents the mass spectrum for fraction 5 of the distillate.

EXAMPLE XIII PATCHOULI PERFUME FORMULATION

The following mixture is prepared:

    ______________________________________                                        Ingredient            Parts by Weight                                         ______________________________________                                        Orange Oil            50                                                      Beramot Oil           20                                                      Lime Oil              100                                                     Neroli Oil            5                                                       4-(4-Methyl-4-hydroxyamyl)                                                                          5                                                       Δ.sup.3 -cyclohexene carboxaldehyde                                     2,3,3A,4,5,7A-hexahydro-6,7A,8,8-                                                                   100                                                     tetramethyl-l,5-methano-1Hinden-                                              1-ol (prepared according to the                                               process of Example I of U.S.                                                  Pat. No. 3,989,760 issued on                                                  November 2, 1976)                                                             1',2',3',4',5',6',7',8'-octahydro                                                                   50                                                      2',3',8',8'-tetramethyl-2'aceto-                                              naphthone isomer mixture produced                                             according to the process of                                                   Example VII of Application for U.S.                                           Letters Pat. No. 434,948 filed                                                on January 21, 1974, now U.S.                                                 Pat. No. 3,911,018 issued on                                                  October 7, 1975                                                               Gamma Methyl Ionone   20                                                      1-acetyl-2,5,5-trimethylcyclo-                                                                      50                                                      heptane produced according to                                                 U.S. Pat. No. 3,869,411 issued                                                on March 4, 1975                                                              Substituted tricyclcodecane                                                                         100                                                     derivatives prepared according                                                to one of Examples I-XII                                                       ##STR109##                                                                   and                                                                            ##STR110##                                                                   produced according to                                                         Example I                                                                      ##STR111##                                                                   and                                                                            ##STR112##                                                                   produced according to                                                         Example II                                                                     ##STR113##                                                                   and                                                                            ##STR114##                                                                   produced according to                                                         Examples III, IV and V                                                         ##STR115##                                                                   and                                                                            ##STR116##                                                                   produced according to                                                         Example VI                                                                     ##STR117##                                                                   and                                                                            ##STR118##                                                                   produced according to                                                         Example VII                                                                    ##STR119##                                                                   and                                                                            ##STR120##                                                                   produced according to                                                         Example VIII                                                                   ##STR121##                                                                   and                                                                            ##STR122##                                                                   produced according to                                                         Example IX                                                                     ##STR123##                                                                   and                                                                            ##STR124##                                                                   produced according to                                                         Example X                                                                      ##STR125##                                                                    ##STR126##                                                                   and                                                                            ##STR127##                                                                   produced according to                                                         Example XI                                                                     ##STR128##                                                                   and                                                                            ##STR129##                                                                   produced according to                                                         Example XII                                                                   ______________________________________                                    

The substituted tricyclodecane derivatives prepared according to one ofExamples I-XII, when added to this formulation in the amount indicated;and also in amounts up to 30% by weight of the total mixture; or inamounts as little as 1.0% by weight of this mixture, imparts aromacharacteristics to this patchouli composition, in addition to thepatchouli aroma as follows:

                  TABLE II                                                        ______________________________________                                        Structure      Fragrance Profile                                              ______________________________________                                         ##STR130##    A strong maple aroma with pumpkin-like and slightly spicy                     undertones                                                     and                                                                            ##STR131##                                                                   produced according to                                                         Example I                                                                      ##STR132##    A fruity, anisic aroma with a raspberry undertone; on                         dry-out, fruity and berry-like.                                and                                                                            ##STR133##                                                                   produced according to                                                         Example II                                                                     ##STR134##    A woody, resinous, camphoraceous patchouli-like aroma                         reminiscent of patchouli alcohol; with oakmoss undertones                     then green, and woody and floral and rosey topnotes.           and                                                                            ##STR135##                                                                   produced according to                                                         Examples III, IV and V.                                                        ##STR136##    A fatty, slightly minty and camphoraceous aroma with pith-                    ike and pumpkin nuances as well as woody and piney under-                     tones.                                                         and                                                                            ##STR137##                                                                   produced according to                                                         Example VI.                                                                    ##STR138##    A green, fruity, creamy, rhubarb stem-like and banana-                        like aroma.                                                    and                                                                            ##STR139##                                                                   produced according to                                                         Example VII.                                                                   ##STR140##    A strong, herbaceous aroma with an oil and spicey, green,                     basil undertone.                                               and                                                                            ##STR141##                                                                   produced according to                                                         Example VIII.                                                                  ##STR142##    A low keyed fruity (banana), spicey (cinnamic), green                         aroma with sweaty and creamy under- tones.                     and                                                                            ##STR143##                                                                   produced according to                                                         Example IX.                                                                    ##STR144##    A bitter, sweet, herbal, petitgrain-like, lavender and                        bergamot aroma profile with floral undertones.                 and                                                                            ##STR145##                                                                   produced according to                                                         Example X.                                                                     ##STR146##    A minty, spicey, fruity aroma with caryophyllene-like,                        cedarwood and sandalwood undertones becoming borneol-                         woody-like on a dry-out.                                        ##STR147##                                                                   and                                                                            ##STR148##                                                                   produced according to                                                         Example XI.                                                                    ##STR149##    A fruity (apple), anisic-like aroma with dry, hay-like and                    erry-like undertones.                                          and                                                                            ##STR150##                                                                   produced according to                                                         Example XII.                                                                  ______________________________________                                    

EXAMPLE XIV PREPARATION OF SOAP COMPOSITIONS PART A

A total of 100 g of soap chips produced from unperfumed sodium basetoilet soap made from tallow and coconut oil is mixed with 1 g of thesubstituted tricyclodecane derivative prepared according to one ofExamples I-XII until a substantially homogeneous composition isobtained. The soap composition manifests an excellent patchouli-likecharacter having aroma nuances and undertones as indicated in Table IIIbelow.

PART B

A total of 100 g of soap chips produced from unperfumed sodium basetoilet soap made from tallow and coconut oil is admixed with 1 g of oneof the perfume compositions set forth in Example XII until asubstantially homogeneous composition is obtained. The soap compositionsmanifest aromas as indicated in Table II, supra, with a characteristicpatchouli aroma.

                  TABLE III                                                       ______________________________________                                        Structure      Fragrance Profile                                              ______________________________________                                         ##STR151##    A strong maple aroma with pumpkin-like and slightly spicy                     undertones                                                     and                                                                            ##STR152##                                                                   produced according to                                                         Example I                                                                      ##STR153##    A fruity, anisic aroma with a raspberry undertone; on                         dry-out, fruity and berry-like.                                and                                                                            ##STR154##                                                                   produced according to                                                         Example II                                                                     ##STR155##    A woody, resinous, camphoraceous patchouli-like aroma                         reminiscent of patchouli alcohol; with oakmoss undertones                     then green, and woody and floral and rosey  topnotes.          and                                                                            ##STR156##                                                                   produced according to                                                         Examples III, IV and V.                                                        ##STR157##    A fatty, slightly minty and camphoraceous aroma with pith-                    ike and pumpkin nuances as well as woody and piney under-                     tones.                                                         and                                                                            ##STR158##                                                                   produced according to                                                         Example VI.                                                                    ##STR159##    A green, fruity, creamy, rhubarb stem-like and banana-                        like aroma.                                                    and                                                                            ##STR160##                                                                   produced according to                                                         Example VII.                                                                   ##STR161##    A strong, herbaceous aroma with an oily and spicey, green,                    basil undertone.                                               and                                                                            ##STR162##                                                                   produced according to                                                         Example VIII.                                                                  ##STR163##    A low keyed fruity (banana), spicey (cinnamic), green                         aroma with sweaty and creamy under- tones.                     and                                                                            ##STR164##                                                                   produced according to                                                         Example IX.                                                                    ##STR165##    A bitter, sweet, herbal, petitgrain-like, lavender and                        bergamot aroma profile with floral undertones.                 and                                                                            ##STR166##                                                                   produced according to                                                         Example X.                                                                     ##STR167##    A minty, spicey, fruity aroma with caryophyllene-like,                        cedarwood and sandalwood undertones becoming borneol-                         woody-like on a dry-out.                                        ##STR168##                                                                   and                                                                            ##STR169##                                                                   produced according to                                                         Example XI.                                                                    ##STR170##    A fruity (apple), anisic-like aroma with dry, hay-like and                    erry-like undertones.                                          and                                                                            ##STR171##                                                                   produced according to                                                         Example XII.                                                                  ______________________________________                                    

EXAMPLE XV PREPARATION OF A DETERGENT COMPOSITION

A total of 100 g of a detergent powder sold under the trademark "RINSO"are mixed with 0.15 g of a perfume composition containing one of themixtures prepared according to Example XIII until a substantiallyhomogeneous composition having patchouli fragrances with aroma nuancesas indicated in Table II is obtained.

EXAMPLE XVI PREPARATION OF A COSMETIC BASE

A cosmetic powder is prepared by mixing 100 g of talcum powder with 0.25g of one of the perfume compositions of Examples XIII in a ball mill. Asecond cosmetic powder is similarly prepared except that the mixtureproduced in Example XIII is replaced with one of the products producedin one of Examples I-XII, that is, one of the substituted tricyclodecanederivatives of one of Examples I-XII. The cosmetic powder containing thematerials of Example XIII have patchouli aromas with dominatingundertones and nuances as indicated in Table II, supra, in Example XIII.The cosmetic powder produced using the materials of one of ExamplesI-XII have patchouli-like characters with aroma nuances as indicated inthe Table IV, below:

                  TABLE IV                                                        ______________________________________                                        Structure       Fragrance Profile                                             ______________________________________                                         ##STR172##     A strong maple aroma with pumpkin-like and slightly spicy                     undertones                                                    and                                                                            ##STR173##                                                                   produced according to                                                         Example I                                                                      ##STR174##     A fruity, anisic aroma with a raspberry undertone; on                         dry-out, fruity and berry-like.                               and                                                                            ##STR175##                                                                   produced according to                                                         Example II                                                                     ##STR176##     A woody, resinous, camphoraceous patchouli-like aroma                         reminiscent of patchouli alcohol; with oakmoss undertones                     then green, and woody and floral and rosey topnotes.          and                                                                            ##STR177##                                                                   produced according to                                                         Examples III, IV and V.                                                        ##STR178##     A fatty, slightly minty and camphoraceous aroma with                          pith- like and pumpkin nuances as well as woody and piney                     under- tones.                                                 and                                                                            ##STR179##                                                                   produced according to                                                         Example VI.                                                                    ##STR180##     A green, fruity, creamy, rhubarb stem-like and banana-                        like aroma.                                                   and                                                                            ##STR181##                                                                   produced according to                                                         Example VII.                                                                   ##STR182##     A strong, herbaceous aroma with an oily and spicey,                           green, basil undertone.                                       and                                                                            ##STR183##                                                                   produced according to                                                         Example VIII.                                                                  ##STR184##     A low keyed fruity (banana), spicey (cinnamic), green                         aroma with sweaty and creamy under- tones.                    and                                                                            ##STR185##                                                                   produced according to                                                         Example IX.                                                                    ##STR186##     A bitter, sweet, herbal, petitgrain-like, lavender and                        bergamot aroma profile with floral undertones.                and                                                                            ##STR187##                                                                   produced according to                                                         Example X.                                                                     ##STR188##     A minty, spicey, fruity aroma with caryophyllene-like,                        cedarwood and sandalwood undertones becoming borneol-                         woody-like on a dry-out.                                       ##STR189##                                                                   and                                                                            ##STR190##                                                                   produced according to                                                         Example XI.                                                                    ##STR191##     A fruity (apple), anisic-like aroma with dry, hay-like                        and berry-like undertones.                                    and                                                                            ##STR192##                                                                   produced according to                                                         Example XII.                                                                  ______________________________________                                    

EXAMPLE XVII LIQUID DETERGENT CONTAINING SUBSTITUTED TRICYCLODECANEDERIVATIVE PREPARED ACCORDING TO ONE OF EXAMPLES I-XII

Concentrated liquid detergents with warm patchouli-like aromas havingundertones and aroma nuances as indicated in Table V, below, containing0.2%, 0.5% and 1.2% of one of the products produced in accordance withExample I-XII (substituted tricyclodecane derivatives) are prepared byadding appropriate quantities of substituted tricyclodecane derivativesas indicated in Table V below to liquid detergents known as P-87. Thewarm patchouli aroma of the liquid detergents increases with increasingconcentrations of substituted tricyclodecane derivatives as indicated inTable V below with increasing aroma nuances as indicated in Table Vbelow:

                  TABLE V                                                         ______________________________________                                        Structure      Fragrance Profile                                              ______________________________________                                         ##STR193##    A strong maple aroma with pumpkin-like and slightly spicy                     undertones.                                                     ##STR194##    A fruity, anisic aroma with a raspberry undertone; on                         dry-out, fruity and berry-like.                                 ##STR195##    A woody, resinous, camphoraceous patchouli-like aroma                         reminiscent of patchouli alcohol; with oakmoss undertones                     then green, and woody and floral and rosey topnotes.            ##STR196##    A fatty, slightly minty and camphoraceous aroma with pith-                    ike and pumpkin nuances as well as woody and piney under-                     tones.                                                          ##STR197##    A green, fruity, creamy, rhubarb stem-like and banana-                        like aroma. -                                                   ##STR198##    A strong, herbaceous aroma with an oily and spicey, green,                    basil undertone.                                                ##STR199##    A low keyed fruity (banana), spicey (cinnamic), green                         aroma with sweaty and creamy under- tones.                      ##STR200##    A bitter, sweet, herbal, petitgrain-like, lavender and                        bergamot aroma profile with floral undertones.                  ##STR201##    A minty, spicey, fruity aroma with caryophyllene-like,                        cedarwood and sandalwood undertones becoming borneol-                         woody-like on a dry-out.                                        ##STR202##    A fruity (apple), anisic-like aroma with dry, hay-like and                    erry-like undertones.                                          ______________________________________                                    

EXAMPLE XVIII PREPARATION OF COLOGNE AND HANDKERCHIEF PERFUME

The compositions of Example XVIII are incorporated in colognes havingconcentrations of 2.0%, 2.5%, 3.0%, 3.5% and 4.0% in 75%, 80%, 85% and90% aqueous ethanol and into handkerchief perfumes in concentrations of15%, 20%, 25%, 30% and 40% (in 80%, 85%, 90% and 95% aqueous ethanol).The use of the compositions of Example XIII affords distinct anddefinitive patchouli aroma having nuances and undertones as indicated inTable II of Example XIII.

EXAMPLE XIX COLOGNE AND HANDKERCHIEF PERFUME

The substituted tricyclodecane derivatives produced by the processes ofany of Examples I-XII are incorporated into perfumes havingconcentrations of 2.0%, 2.5%, 3.0%, 4.5% and 5.0% in 75%, 80%, 85% and95% aqueous ethanol; into handkerchief perfumes at concentrations of 8%,10%, 12%, 15% and 25% (in 80%, 90%, and 95% aqueous ethanol). Each ofthe substituted tricyclodecane derivatives produced according to ExampleI-XII afford distinct and definitive warm patchouli-like aromas withvarious nuances and undertones as indicated in Table VI to thehandkerchief perfumes and to colognes.

                  TABLE VI                                                        ______________________________________                                        Structure       Fragrance Profile                                             ______________________________________                                         ##STR203##     A strong maple aroma with pumpkin-like and slightly spicy                     undertones                                                    and                                                                            ##STR204##                                                                   produced according to                                                         Example I                                                                      ##STR205##     A fruity, anisic aroma with a raspberry undertone; on                         dry-out, fruity and berry-like.                               and                                                                            ##STR206##                                                                   produced according to                                                         Example II                                                                     ##STR207##     A woody, resinous, camphoraceous patchouli-like aroma                         reminiscent of patchouli alcohol; with oakmoss undertones                     then green, and woody and floral and rosey  topnotes.         and                                                                            ##STR208##                                                                   produced according to                                                         Examples III, IV and V.                                                        ##STR209##     A fatty, slightly minty and camphoraceous aroma with                          pith- like and pumpkin nuances as well as woody and piney                     under- tones.                                                 and                                                                            ##STR210##                                                                   produced according to                                                         Example VI.                                                                    ##STR211##     A green, fruity, creamy, rhubarb stem-like and banana-                        like aroma.                                                   and                                                                            ##STR212##                                                                   produced according to                                                         Example VII.                                                                   ##STR213##     A strong, herbaceous aroma with an oily and spicey, gren,                     basil undertone.                                              and                                                                            ##STR214##                                                                   produced according to                                                         Example VIII.                                                                  ##STR215##     A low keyed fruity (banana), spicey (cinnamic), green                         aroma with sweaty and creamy under- tones.                    and                                                                            ##STR216##                                                                   produced according to                                                         Example IX.                                                                    ##STR217##     A bitter, sweet, herbal, petitgrain-like, lavender and                        bergamot aroma profile with floral undertones.                and                                                                            ##STR218##                                                                   produced according to                                                         Example X.                                                                     ##STR219##     A minty, spicey, fruity aroma with caryophyllene-like,                        cedarwood and sandalwood undertones becoming borneol-                         woody-like on a dry-out.                                       ##STR220##                                                                   and                                                                            ##STR221##                                                                   produced according to                                                         Example XI.                                                                    ##STR222##     a fruity (apple), anisic-like aroma with dry, hay-like                        and berry-like undertones.                                    and                                                                            ##STR223##                                                                   produced according to                                                         Example XII.                                                                  ______________________________________                                    

EXAMPLE XX TOBACCO FLAVOR FORMULATIONS

Cigarettes are produced using the following tobacco formulations:

    ______________________________________                                        Ingredients    Parts by Weight                                                ______________________________________                                        Bright         40.1                                                           Burley         24.9                                                           Maryland        1.1                                                           Turkish        11.6                                                           Stem (flue-cured)                                                                            14.2                                                           Glycerine       2.8                                                           H.sub.2 O       5.3                                                           ______________________________________                                    

At the rate of 0.2%, the following tobacco flavor formulation is appliedto all of the cigarettes produced with the above tobacco formulation:

    ______________________________________                                        Ingredients      Parts by Weight                                              ______________________________________                                        Ethyl butyrate   .05                                                          Ethyl valerate   .05                                                          Maltol           2.00                                                         Cocoa Extract    26.00                                                        Coffee Extract   10.00                                                        Ethyl Alcohol (95%)                                                                            20.00                                                        H.sub.2 O        41.90                                                        ______________________________________                                    

Two portions of 50% of the cigarettes at levels of 10 and 20 ppm,substituted tricyclodecane derivatives as indicated in Table VII below.These cigarettes are hereinafter called "experimental" cigarettes andthe cigarettes without the substituted tricyclodecane derivatives arehereinafter called "control" cigarettes. The "control" and"experimental" cigarettes are then evaluated by paired comparison andthe results are as follows:

a. In aroma, the "experimental" cigarettes are all found to be morearomatic with nuances as indicated in Table VII below;

b. In smoke flavor, the "experimental" cigarettes are found to be morearomatic, more sweet with bitter, richer and less harsh in the mouth andmore cigarette tobacco-like than the "control" cigarettes.

The "experimental" cigarettes containing 20 ppm of each of the compoundsprepared according to Examples I-XII as indicated in Table VII below arefound to be woody, slightly chemical and mouth coating in the smokeflavor.

                  TABLE VII                                                       ______________________________________                                        Structure       Tobacco Flavor Profile                                        ______________________________________                                         ##STR224##     A sweet, fruity, citrusy aroma and taste prior to and on                      smoking in the main stream and the side stream.               and                                                                            ##STR225##                                                                   produced according to                                                         Example I                                                                      ##STR226##     A sweet, woody, spicey, herba- ceous aroma and taste both                     prior to and on smoking in the main stream and side                           stream.                                                       and                                                                            ##STR227##                                                                   produced according to                                                         Example II.                                                                    ##STR228##     A sweet, herbaceous, spicey, hay-clover-like and woody                        aroma and taste profile both prior to and on smoking in                       the main stream and the side stream.                          and                                                                            ##STR229##                                                                   produced according to                                                         Examples III, IV and V.                                                        ##STR230##     A sweet, creamy and buttery aroma and taste both prior to                     and on smoking in the main stream and in the side                             stream.                                                       and                                                                            ##STR231##                                                                   produced according to                                                         Example VI.                                                                    ##STR232##     A sweet, fruity, plum-like, fatty, cucumber-like aroma                        and taste both prior to and on smoking in the main stream                     nd in the side stream.                                        and                                                                            ##STR233##                                                                   produced according to                                                         Example VII.                                                                   ##STR234##     A cocoa-like, sweet, floral and green aroma prior to                          smoking and a sweet, floral and green aroma on smoking in                     the main stream and in the side stream.                       and                                                                            ##STR235##                                                                   produced according to                                                         Example VIII.                                                                  ##STR236##     A sweet, floral, carnation, creamy aroma and taste prior                      to smoking and a green, floral aroma and taste on smoking                     n the main stream and in the side stream.                     and                                                                            ##STR237##                                                                   produced according to                                                         Example IX.                                                                    ##STR238##     A sweet, green, cucumber, melon, pea-like aroma and taste                     both prior to and on smoking in the main stream and the                       side stream.                                                  and                                                                            ##STR239##                                                                   produced according to                                                         Example X.                                                                     ##STR240##     An earthy, grapefruit peel- like, albedo, camphoraceous                       aroma and taste both prior to and on smoking in the main                      stream and in the side stream.                                 ##STR241##                                                                   and                                                                            ##STR242##                                                                   produced according to                                                         Example XI.                                                                    ##STR243##     A sweet, woody, camphoraceous, spicey aroma and taste                         profile  both prior to and on smoking in the main stream                      and in the side stream.                                       and                                                                            ##STR244##                                                                   produced according to                                                         Example XII.                                                                  ______________________________________                                    

All cigarettes both "control" and "experimental" are evaluated for smokeflavor with 20 mm cellulose acetate filter. In summary, each of thematerials of Examples I-XII enhance the tobacco-like tastes of theblended cigarettes.

EXAMPLE XXI

The following chocolate basic formulation is prepared:

    ______________________________________                                        Ingredients           Parts by Weight                                         ______________________________________                                        Dimethoxy phenol (10% in propylene                                                                  0.5                                                     glycol)                                                                       Amyl acetate          0.1                                                     Amyl cinnamate        0.1                                                     Gamma butyryl lactone 0.2                                                     Furfural              0.05                                                    Benzaldehyde          0.05                                                    Trimethyl pyrazine    0.05                                                    Phenyl acetic acid    0.35                                                    Isovaleraldehyde      1.6                                                     Ethyl maltol          12.0                                                    Ethyl vanillin        20.0                                                    1,2-Propylene Glycol USP                                                                            165.0                                                   Nestle Cocoa Extract  800.0                                                   ______________________________________                                    

This basic chocolate flavor is divided into two parts. To the first partis added at the rate of 0.05 ppm the substituted tricyclodecanederivative prepared according to Example II at the rate of 0.05%. To thesecond part, nothing is added. Both flavors are compared at the rate of200 ppm. The flavor with the ingredient of Example II has additionalvery characteristic cocoa butter-like notes both in aroma and taste.These notes are completely missing in the basic chocolate flavor thatdoes not contain the additional material prepared according to ExampleII. Therefore, the flavor with the material of Example II is preferredas having the desired cocoa butter characteristic.

EXAMPLE XXII BASIC WALNUT FLAVOR FORMULATION

The following basic walnut flavor formulation is prepared:

    ______________________________________                                        Ingredients           Parts by Weight                                         ______________________________________                                        Cyclotene             4                                                       Vanillin              1                                                       Butyl isovalerate     2                                                       Benzaldehyde          6                                                       2,3-Diethyl pyrazine 10% in food grade                                                              2                                                       ethyl alcohol                                                                 Ethyl-2-methyl valerate                                                                             2                                                       Gamma Butyrolactone   20                                                      Gamma Hexenyl lactone 10                                                      2,4-Decadienal (0.1% in food grade                                                                  0.5                                                     ethyl alcohol)                                                                2,4-Heptadienal (0.1% in food grade                                                                 0.5                                                     ethyl alcohol)                                                                Butylidene phthalide  2                                                       Propylene glycol USP  95                                                      ______________________________________                                    

The foregoing flavor formulation is divided into two parts. To the firstpart at the rate of 5% is added the substituted tricyclodecanederivative prepared according to Example V. To the second part, nothingis added. Both flavors are compared by a bench panel at the rate of 20ppm in water. The flavor with the addition of the product producedaccording to Example V has a pleasant, fresh walnut kernel taste with afresh walnut aroma not present in the basic walnut flavor formulation.Therefore the flavor with the material produced according to Example Vis preferred as being much more characteristic in walnut flavor by thebench panel (unanimous preference). The flavor is also evaluated at 1ppm and the same unanimous preference is obtained.

EXAMPLE XXIII BASIC ORAL HYGIENE FLAVOR FORMULATION

The following basic oral hygiene flavor formulation is prepared:

    ______________________________________                                        Ingredients     Parts by Weight                                               ______________________________________                                        Peppermint oil  89.0                                                          Spearmint oil   2.0                                                           Clove oil       1.0                                                           Anethole        2.0                                                           Cardamon oil    0.1                                                           Wintergreen oil 5.0                                                           Cinnamic aldehyde                                                                             0.9                                                           ______________________________________                                    

The basic oral hygiene flavor formulation is now divided into two parts.To the first part at the rate of 10% is added the substitutedtricyclodecane derivative prepared according to Example VIII, the allylether. To the second part, nothing is added. The flavor with theaddition of the material produced according to Example VIII has afresher herbaceous aroma and flavor characteristic with anis seed notes.The peppermint characteristics also appear to be enhanced. Therefore,the flavor with the material produced according to Example VIII ispreferred by the bench panel.

EXAMPLE XXIV PREPARATION OF A SOAP COMPOSITION

One hundred grams of soap chips are produced according to Example V ofU.S. Pat. No. 4,058,487 issued on Nov. 15, 1977, as follows:

"The sodium salt of an equal mixture of C₁₀ -C₁₄ alkane sulfonate (95%active), 40 pounds, is dissolved in a mixture of 80 pounds of anhydrousisopropanol and 125 pounds of deionized water at 150° F. In this mixtureis dissolved 10 pounds of partially hydrogenated cocoanut oil fattyacids and 15 pounds of sodium mono-C₁₄ alkyl maleate, and the pH of thissolution is adjusted to 6.0 by the addition of a small amount of 50%aqueous solution of sodium hydroxide. The isopropanol is distilled off,and the remaining aqueous solution is drum dried. The resulting solidactives are then blended in a chip mixture with 10 pounds water, 0.2pounds titanium hydroxide and 0.7 pounds of one of the materialsproduced according to Examples I-XII as enumerated in the Table below.The chips are then plodded into logs, cut to size and finally stampedinto bars having a pH of approximately 6.9."

Each of the perfumed soaps manifests aromas with strong patchouli notesas indicated in the Table VIII below:

                  TABLE VIII                                                      ______________________________________                                        Structure      Fragrance Profile                                              ______________________________________                                         ##STR245##    A strong maple aroma with pumpkin-like and slightly spicy                     undertones                                                     and                                                                            ##STR246##                                                                   produced according to                                                         Example I                                                                      ##STR247##    A fruity, anisic aroma with a raspberry undertone; on                         dry-out, fruity and berry-like.                                and                                                                            ##STR248##                                                                   produced according to                                                         Example II                                                                     ##STR249##    A woody, resinous, camphoraceous patchouli-like aroma                         reminiscent of patchouli alcohol; with oakmoss undertones                     then green, and woody and floral and rosey topnotes.           and                                                                            ##STR250##                                                                   produced according to                                                         Examples III, IV and V.                                                        ##STR251##    A fatty, slightly minty and camphoraceous aroma with pith-                    ike and pumpkin nuances as well as woody and piney under-                     tones.                                                         and                                                                            ##STR252##                                                                   produced according to                                                         Example VI.                                                                    ##STR253##    A green, fruity, creamy, rhubarb stem-like and banana-                        like aroma.                                                    and                                                                            ##STR254##                                                                   produced according to                                                         Example VII.                                                                   ##STR255##    A strong, herbaceous aroma with an oily and spicey, green,                    basil undertone.                                               and                                                                            ##STR256##                                                                   produced according to                                                         Example VIII.                                                                  ##STR257##    A low keyed fruity (banana), spicey (cinnamic), green                         aroma with sweaty and creamy under- tones.                     and                                                                            ##STR258##                                                                   produced according to                                                         Example IX.                                                                    ##STR259##    A bitter, sweet, herbal, petitgrain-like, lavender and                        bergamot aroma profile with floral undertones.                 and                                                                            ##STR260##                                                                   produced according to                                                         Example X.                                                                     ##STR261##    A minty, spicey, fruity aroma with caryophyllene-like,                        cedarwood and sandalwood  undertones becoming borneol-                        woody-like on a dry-out.                                        ##STR262##                                                                   and                                                                            ##STR263##                                                                   produced according to                                                         Example XI.                                                                    ##STR264##    A fruity (apple), anisic-like aroma with dry, hay-like and                    erry-like undertones.                                          and                                                                            ##STR265##                                                                   produced according to                                                         Example XII.                                                                  ______________________________________                                    

EXAMPLE XXV PREPARATION OF A DETERGENT COMPOSITION

A total of 100 pounds of a detergent powder prepared according to U.S.Pat. No. 4,058,472 and containing 5% by weight of the sodium salts of amixture of sulfonated C₁₄ -C₁₈ alkyl catechol as a surface activecomponent, the mixture being 60 parts by weight of mono-C₁₄ -C₁₈ alkylcatechol and 40 parts by weight of di-C₁₄ -C₁₈ alkyl catechol, 35% ofsodium tetrapyrophosphate, 30% of sodium silcate, 20% of sodiumcarbonate, 3% of sodium carboxymethyl cellulose and 7% of starch ismixed with 0.15 grams of one of the substituted tricyclodecanederivatives produced according to one of Examples I-XII as set forth inTable IX below until a substantially homogeneous composition isobtained. Each of the compositions have excellent patchouli aromas withnuances and undertones as enumerated in the Table below:

    ______________________________________                                        Structure       Fragrance Profile                                             ______________________________________                                         ##STR266##     A strong maple aroma with pumpkin-like and slightly spicy                     undertones                                                    and                                                                            ##STR267##                                                                   produced according to                                                         Example I                                                                      ##STR268##     A fruity, anisic aroma with a raspberry undertone; on                         dry-out, fruity and berry-like.                               and                                                                            ##STR269##                                                                   produced according to                                                         Example II                                                                     ##STR270##     A woody, resinous, camphoraceous patchouli-like aroma                         reminiscent of patchouli alcohol; with oakmoss undertones                     then green, and woody and floral and rosey topnotes.          and                                                                            ##STR271##                                                                   produced according to                                                         Examples III, IV and V.                                                        ##STR272##     A fatty, slightly minty and camphoraceous aroma with                          pith- like and pumpkin nuances as well as woody and piney                     under- tones.                                                 and                                                                            ##STR273##                                                                   produced according to                                                         Example VI.                                                                    ##STR274##     A green, fruity, creamy, rhubarb stem-like and banana-                        like aroma.                                                   and                                                                            ##STR275##                                                                   produced according to                                                         Example VII.                                                                   ##STR276##      A strong, herbaceous aroma with an oily and spicey,                          green, basil undertone.                                       and                                                                            ##STR277##                                                                   produced according to                                                         Example VIII.                                                                  ##STR278##     A low keyed fruity (banana), spicey (cinnamic), green                         aroma with sweaty and creamy under- tones.                    and                                                                            ##STR279##                                                                   produced according to                                                         Example IX.                                                                    ##STR280##     A bitter, sweet, herbal, petitgrain-like, lavender and                        bergamot aroma profile with floral undertones.                and                                                                            ##STR281##                                                                   produced according to                                                         Example X.                                                                     ##STR282##     A minty, spicey, fruity aroma with caryophyllene-like,                        cedarwood and sandalwood undertones becoming borneol-                         woody-like on a dry-out.                                       ##STR283##                                                                   and                                                                            ##STR284##                                                                   produced according to                                                         Example XI.                                                                    ##STR285##     A fruity (apple), anisic-like aroma with dry, hay-like                        and berry-like undertones.                                    and                                                                            ##STR286##                                                                   produced according to                                                         Example XII.                                                                  ______________________________________                                    

What is claimed is:
 1. A mixture of compounds defined according to thestructure: ##STR287## produced according to the process comprising thesteps, in sequential order of:(i) intimately admixing in the presence ofa Lewis acid catalyst or a protonic acid catalyst a mixture of methylsubstituted bicyclopentadienes having the structures: ##STR288## with analkanoic acid anhydride or an alkanoic acid at a temperature of fromabout 0° C. up to about 50° C. and a concentration of acid catalyst offrom 0.01 mole percent up to 1 mole percent based on the weight ofreaction mass whereby a product containing a major proportion of estersis formed; (ii) hydrolyzing the resulting product containing a majorproportion of esters with a hydrolysis reagent whereby a mixturecontaining a major proportion of alcohols is formed, said hydrolysisbeing carried out using as a hydrolysis reagent from 10 up to 50% byweight alkali metal hydroxide; the mole ratio of alkali metalhydroxide:mixture of ester derivatives being from 1 up to 2 moles ofalkali metal hydroxide per mole of ester at a temperature of from about40° C. up to about 120° C.; and then (iii) oxidizing the resultingmixture of alcohols with an oxidation reagent selected from the groupconsisting of sodium dichromate, Jones reagent, chromium trioxide,copper chromite, and pyridinium chloro chromate at a temperature in therange of from 20° C. up to 220° C. according to the reaction: ##STR289##2. The product of claim 1 wherein in the process the oxidation reagentused is copper chromite and the temperature of reaction is 180°-220° C.at atmospheric pressure.
 3. The product of claim 1 wherein in theprocess for preparing said product the oxidation reagent is sodiumdichromate, Jones reagent or chromium trioxide and the reactiontemperature is in the range of from about 20° up to about 80° C.; andthe reaction is carried out in the presence of a solvent selected fromthe group consisting of toluene and methylene dichloride.
 4. The productof claim 1 wherein in the process, the oxidation reagent is pyridiniumchloro chromate and the reaction temperature is in the range of betweenabout 25° C. and about 100° C.